Aluminum metal has been produced for 90 years in the Hall cell by electrolysis of alumina in a molten cryolite salt electrolyte bath operating at temperatures in the range of 900.degree.-1000.degree. C. The reactivity of the molten cryolite, the need for excellent electrical conductivity, and cost considerations have limited the choice of materials for the electrodes and cell walls to the various allotropic forms of carbon.
Typically the Hall cell is a shallow vessel, with the floor forming the cathode, the side walls a rammed coke-pitch mixture, and the anode a carbon block suspended in the bath at an anode-cathode separation of a few centimeters. The anode is typically formed from a pitch-calcined petroleum coke blend, prebaked to form a monolithic block of amorphous carbon. The cathode is typically formed from a pre-baked pitch-calcined anthracite or coke blend, with cast-in-place iron over steel bar electrical conductors in grooves in the bottom side of the cathode.
During operation of the Hall cell, only about 25% of the electricity consumed is used for the actual reduction of alumina to aluminum, with approximately 40% of the current consumed by the voltage drop caused by the resistance of the bath. The anode-cathode spacing is usually about 4-5 cm., and attempts to lower this distance result in an electrical discharge from the cathode to the anode through aluminum droplets suspended in the bath.
The molten aluminum is present as a pad in the cell, but is not a quiescent pool due to the factors of preferential wetting of the carbon cathode surface by the cryolite melt in relation to the molten aluminum, causing the aluminum to form droplets; and the erratic movements of the molten aluminum from the strong electromagnetic forces generated by the high current density.
The wetting of a solid surface in contact with two immiscible liquids is a function of the surface free energy of the three surfaces, in which the carbon cathode is a low energy surface and consequently is not readily wet by the liquid aluminum. The angle of a droplet of aluminum at the cryolite-aluminum-carbon junction is governed by the relationship ##EQU1## where .alpha..sub.12, .alpha..sub.13, and .alpha..sub.23 are the surface free energies at the aluminum-carbon, cryolite-carbon, and cryolite-aluminum boundaries, respectively.
If the cathode were a high energy surface, such as would occur if it were a ceramic instead of carbon, it would have a higher contact angle and better wettability with the liquid aluminum. This in turn would tend to smooth out the surface of the liquid aluminum pool and lessen the possibility of interelectrode discharge allowing the anode-cathode distance to be lowered and the thermodynamic efficiency of the cell improved, by decreasing the voltage drop through the bath.
Typically, amorphous carbon is a low energy surface, but also it is quite durable, lasting for several years duration as a cathode, and relatively inexpensive. However, a cathode or a cathode component such as a TiB.sub.2 stud which has better wettability and would permit closer anode-cathode spacing by reducing movement of molten aluminum could improve the thermodynamic efficiency and be very cost-effective.
Several workers in the field have developed refractory high free energy material cathodes. U.S. Pat. No. 2,915,442, Lewis, Dec. 1, 1959, claims a process for production of aluminum using a cathode consisting of the borides, carbides, and nitrides of Ti, Zr, V, Ta, Nb, and Hf. U.S. Pat. No. 3,028,324, Ransley, Apr. 3, 1962, claims a method of producing aluminum using a mixture of TiC and TiB.sub.2 as the cathode. U.S. Pat. No. 3,151,053, Lewis, Sept. 29, 1964, claims a Hall cell cathode conducting element consisting of one of the carbides and borides of Ti, Zr, Ta and Nb. U.S. Pat. No. 3,156,639, Kibby, Nov. 10, 1964, claims a cathode for a Hall cell with a cap of refractory hard metal and discloses TiB.sub.2 as the material of construction. U.S. Pat. No. 3,314,876, Ransley, Apr. 18, 1967, discloses the use of TiB.sub.2 for use in Hall cell electrodes. The raw materials must be of high purity particularly in regard to oxygen content, Col. 1, line 73-Col. 2, line 29; Col. 4, lines 39-50, Col. 8, lines 1-24. U.S. Pat. No. 3,400,061, Lewis, Sept. 3, 1968 discloses a cathode comprising a refractory hard metal and carbon, which may be formed in a one-step reaction during calcination. U.S. Pat. No. 4,071,420, Foster, Jan. 31, 1978, discloses a cell for the electrolysis of a metal component in a molten electrolyte using a cathode with refractory hard metal TiB.sub.2 tubular elements protruding into the electrolyte. Ser. No. 043,242, Kaplan et al. (Def. Pub.), filed May 29, 1979, discloses Hall cell bottoms of TiB.sub.2. Canada Pat. No. 922,384, Mar. 6, 1973, discloses in situ formation of TiB.sub.2 during manufacture of arc furnace electrodes. Belgian Pat. No. 882,992, PPG Ind., Oct. 27, 1980, discloses TiB.sub.2 cathode plates.
Our co-pending applications, Ser. No. 186,181 now U.S. Pat. No. 4,376,029, and Ser. No. 186,182, now abandoned filed Sept. 11, 1980, disclose related subject matter.